【作者】 李海晏；

【导师】 叶瑛； 夏枚生；

【作者基本信息】 浙江大学 ， 矿物学、岩石学、矿床学， 2012， 博士

【摘要】 本研究着力解决固体废弃物贝壳资源化利用难题及评估我国贝类养殖对海洋碳循环的贡献。以废弃贝壳为原料制备了生物填料,并对其表介面特性进行了研究。将制备的生物填料填充到聚丙烯和聚氯乙烯中,对贝壳填料聚丙烯复合材料力学性能和结晶性能以及贝壳填料聚氯乙烯复合材料力学性能进行了考察。对厚壳贻贝壳粉体的抗霉性能进行了研究。主要研究内容和结果如下：(1)以2001年到2010年的年平均产量计算、评估了贝类捕获和养殖的碳沉积能力,并评估了其碳沉积潜力。我国近十年贝类年产量稳定在1100万吨以上,其中海水养殖贝类约占87.34%。贝类养殖和捕获总产量的碳沉积和海水养殖产量的碳沉积量分别为58.57、51.15万吨／年,碳沉积能力分别相当于122.28、106.78万公顷的造林,可分别减少大气C02增加量的0.0125%、0.0109%。(2)以废弃珍珠贝壳为原料,经去除角质层、分离棱柱层,得到珍珠层。然后采用机械研磨得到生物填料(ZZB),对其表介面特性研究表明,其主要成分为文石型碳酸钙,成片状,粒径大小约为100～500nm,有机物含量约为3.87%,热稳定性良好。表面元素平均原子含量(%)为Ca(14.43)、C(33.54)、O(50.40)、N(1.62),其中有机物中各元素实际含量原子比(%)为：C(68.64)、O(25.54)、N(5.82)；表面含有(CH2)n-、MeCH2NH2、MeCOOH等有机基团。ZZB粉体具有亲水、亲油的双亲性,对正庚烷浸润,对水的接触角约为23.40。(3)以废弃河蚌壳为原料,去除角质层,分离棱柱层和珍珠层,分别机械研磨得到珍珠层生物填料(HBZZC)和棱柱层生物填料(HBLZC)。它们的主要成分都为文石型碳酸钙,热稳定性良好,但HBZZC粉体成片状,粒径大小为40-1000nm,有机物含量约为4.34%,而HBLZC粉体成柱状、长条状,粒径分布范围为1～10μm,有机物含量约为2.20%。HBZZC粉体表面元素平均原子含量(%)为Ca(8.71),C(45.17),O(43.79),N(2.33),其中有机物中各元素实际含量原子比(%)约为：C(64.59),O(31.28),N(4.13)；HBLZC粉体表面元素平均原子含量(%)为Ca(12.10),C(33.63),O(51.35),N(2.93),其中有机物中各元素实际含量原子比(%)约为：C(54.49),O(38.09),N(7.42)。二者都具有亲水、亲油双亲性,都对正庚烷浸润,对水的接触角分别为24.5°和32°。(4)以废弃厚壳贻贝壳、紫贻贝壳为原料分别制备的生物填料YBCC和ZYBCC粉体,其主要成分都为文石型碳酸钙,成片状,有机物含量分别约为2.04%、2.68%,热稳定性良好。YBCC、ZYBCC粉体对mm/YBCC、mm/ZYBCC复合材料具有增强作用,当YBCC、ZYBCC填充比例为3%时,mm/YBCC、 mm/ZYBCC复合材料的屈服强度达最大,分别比mm高了11.1%、6.8%。YBCC、 ZYBCC对mm具有异相成核作用,对mm结晶度与熔点影响较小,可诱导mm形成p-晶,提高mm/YBCC、mm/ZYBCC复合材料结晶度。YBCC对mVC/YBCC复合材料力学性能的影响与无机改性碳酸钙(方解石型碳酸钙)类似,无显著差异。(5)将厚壳贻贝壳粉体添加到聚乙烯醇(mVA)中制成涂料试板,研究其抗霉性能,只在涂料试板表面边缘上有少量的霉菌生长,生霉面积为1%,长霉等级0<1级,具有较好的抗霉作用。更多还原

【Abstract】 This study was aimed to settle the resource utilization problem of the waste shellfish shell and evaluate the contribution of shellfish culture in china on the ocean carbon cycle. Several kinds of bio-fillers were prepared from the waste shellfish shell and their surface properties were characterized. The mechanical properties and crystallization properties of molypropylene/calcium carbonate composite materials and polyvinyl chloride/calcium carbonate composite materials were researched. The anti-fungi performance of the shellfish shell powder was studied too. The main contents and results were as follows:(1) motential ability of carbon deposition of shellfish of China was calculated and evaluated by the10year average yield of fishing shellfish and culturing shellfish production from2001year to2010year based on China Fishery Statistics Yearbook. Analysis shows that the total yield of shellfish is stable and more than110million tons with an increasing trend and the mariculture shellfish is account for about87.34%. The total carbon deposition of shellfish aquaculture and capture and the amount of carbon deposition of the mariculture shellfish are approximately585.7,511.5thousand tons per year which are equivalent to about1222.8and1067.8thousand hectares afforestation for carbon deposition and can reduce the increasing amount of CO2in the atmosphere by approximately0.0125%and0.0109%respectively. Carbon deposition rates of oyster, clam, scallop and mussel are1.573,0.388,0.301and1.039tons C ha-1yr-1separately. The carbon deposition rates of oyster and mussel with consumption of economic value are higher than the forest (0.479tons C ha-1yr-1), but lower than the coral reefs (1.8tons C ha-1yr-1). The effect of using the shellfish for carbon deposition is superior to capture and archive CO2directly into deep sea though carbon capture and storage engineering. Freshwater culture shellfish and mariculture shellfish can create carbon credit opportunities by2.684million yuan and127.112million yuan separately per year in China.(2) Granule of pearl oyster shell bio-filler (ZZB) was prepared from waste pearl oyster shell by removing cuticle, separating prismatic layer and the left nacreous layer was grinded. The characterization results of ZZB show that the mainly composition of ZZB is aragonite (CaCO3) platelets and the particle size distribution range of ZZB powder is from100nm to500nm, the proportion of organic components of ZZB is about3.87%and with a good thermal stability. Calcium, carbon, oxygen and nitrogen contents on the surface of ZZB determined by XmS are14.43%,33.54%,50.40%and1.62%respectively, while the actual contents of carbon, oxygen and nitrogen of the organic matter within the ZZB powder are approximately68.64%,25.54%and5.82%separately; organic groups of (CH2)n-, MeCH2NH2and MeCOOH may be existing on its surface. Both lipophilic and hydrophilic properties of ZZB powder are significantly. N-heptane spreads out on the ZZB powder and the water contact angle is about23.4°.(3) Removing cuticle, separating nacreous layer and prismatic layer of freshwater mussel shell, then the bio-filler HBZZC and HBLZC were prepared by mechanical grinding from the nacreous layer and prismatic layer of thick shell mussel (mytilus coruscus gould) shell respectively. The characterization results of HBZZC and HBLZC show that the mainly compositions of both of the HBZZC and HBLZC filler are aragonite (CaCO3) platelets and the particle size distribution ranges of HBZZC and HBLZC powder are40-1000nm and1～10μm VHSDUDHOY, thH proportions of organic components of HBZZC and HBLZC particles are about4.34%and2.20%respectively and both of them are being with a good thermal stability. Calcium, carbon, oxygen and nitrogen contents on the surface of HBZZC determined by XmS are8.71%,45.17%,43.79%and2.33%respectively, while the actual contents of carbon, oxygen and nitrogen of the organic matter within the HBZZC powder are approximately64.59%,31.28%and4.13%separately. Calcium, carbon, oxygen and nitrogen contents on the surface of HBLZC determined by XmS are12.10%,33.63%,51.35%and2.93%respectively, while the actual contents of carbon, oxygen and nitrogen of the organic matter within the HBLZC powder are approximately54.49%,38.09%and7.42%separately. Both of hydrophilic property and lipophilic property of HBZZC and HBLZC powder are significantly. N-heptane spreads out on the HBZZC and HBLZC powder and the water contact angles are about24.5°and32°respectively.(4) Bio-filler YBCC and ZYBCC were prepared from waste thick shell mussel (mytilus coruscus gould) shell and mytilus edulis shell by removing cuticle, crushing, grinding and shearing emulsification and was introduced as a filler to reinforce polypropylene (PP) and Polyvinyl chloride (PVC). The characterization results of YBCC and ZYBCC show that the mainly compositions of both YBCC and ZYBCC are aragonite (CaCO3) platelets, the proportion of organic components of YBCC and ZYBCC are about2.04%and2.68%respectively and being with a good thermal stability. The mechanical behavior of PP/YBCC and PP/ZYBCC composites show a higher yield strain, yield strength, tensile strength and elongation at break than traditional commercial calcium carbonate (CMCC) filled PP. The yield strength of PP/YBCC and PP/ZYBCC composites with3%YBCC and ZYBCC are improved by about11.1%and6.8%respectly. YBCC and ZYBCC can promote the heterogeneous nucleation for PP crystallization and the formation β-crystalline PP. The mechanical behavior of PP/PVC composites show no significant differences with the traditional commercial calcium carbonate (CMCC) filled PP.(5) The YBCC powder was added into the Polyvinyl alcohol (PVA) for preparing the coating test plate for researching its anti-mold properties. The experimental results show that the anti-mold properties of the YBCC powder are well, the mildew area of the coating test plate surface is1%and the fungi-growth grade is0<1.更多还原